UNDERSTANDING COLD CAP - GLASS MELT CONVERSION FOR WASTE - - PowerPoint PPT Presentation

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UNDERSTANDING COLD CAP - GLASS MELT CONVERSION FOR WASTE VITRIFICATION AT THE HANFORD SITE, USA Jessica C. Rigby 1 , Anthony M. T. Bell 1 and Paul A. Bingham 1 , Ashutosh Goel 2 , John S. McCloy 3 , John D. Vienna 4 , Kevin M. Fox 5 , David K.

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SLIDE 1

UNDERSTANDING COLD CAP - GLASS MELT CONVERSION FOR WASTE VITRIFICATION AT THE HANFORD SITE, USA

Jessica C. Rigby1, Anthony M. T. Bell1 and Paul A. Bingham1 , Ashutosh Goel2, John S. McCloy3, John D. Vienna4, Kevin M. Fox5, David K. Peeler5, Donna P. Guillen6

1Materials and Engineering Research Institute, Sheffield Hallam University, Howard Street,

S1 1WB, UK; 2Rutgers University, USA; 3Washington State University, USA; 4Pacific Northwest National Laboratory, USA 5Savanah River National Laboratory, USA; 6Idaho National Laboratory, USA

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SLIDE 2

2 200,000m3 of radioactive defence wastes stored in 177 steel tanks In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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The Hanford Site, WA

65% of total US plutonium production including the Manhattan Project and Cold War

The Solution: Vitrification at Hanford's Waste Treatment Plants (WTPs). Final glass wasteform to be stored in geological repositories.

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SLIDE 3

In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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Forming the Cold Cap

Inside the Joule-Heated Ceramic Melter(P. R. Hrma, Chun, Pierce, & Pokorný, 2013)

  • Waste and glass forming

chemicals are fed into the top

  • f the melter.
  • Electrodes heat the melt to

1150oC

  • Forced bubbling homogenises

the melt

  • Glass is discharged through

port to cooling canisters

  • In

Incoming feed creates a batch bl blank nket; the he co cold ca cap.

3

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SLIDE 4

4

Inside the Cold Cap

  • Evaporation of Water
  • Dehydration
  • Decarbonation and denitration
  • Low-viscosity melt forming
  • Formation of continuous glass

forming melt

  • Primary foaming caused by

mostly CO2 evolution

  • Primary foam collapse
  • Melt viscosity increases
  • Sec

Secondary foaming

  • Dissolution of Quartz
  • Re

Redox reactions and evolution of SO2

Cold cap profile showing temperature regions. Adapted from (Xu et al., 2016)

Bo Boiling slurry Op Open porosity reaction layer Gl Glass melt Fo Foam Layer

100 100oC 400 400oC 700 700oC 800 800oC 900 900oC 1000 1000oC 1100 1100oC 1150 1150oC

To what extent does the redox state of the melt effect the foaming?

In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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SLIDE 5

Stages of Melting Study

5

Sample Preparation

Feed Expansion Tests Laboratory Scale Melter

How can we analyse the cold cap?

  • In situ observation
  • Mathematical modelling
  • Representative samples

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800oC 900oC 1000oC 1100oC 1150oC

media

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SLIDE 6
  • Generic, simplified waste compositions
  • Specific waste streams with extreme levels
  • f waste oxides:

HLW-A19

In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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6 Ra Raw Material al Ox Oxide HL HLW- A1 A19/100g wt wt% Al(OH)3 Al2O3 37.18 24.53 H3BO3 B2O3 34.16 19.41 CaCO3 CaO 1.09 0.61 Fe(OH)3 Fe2O3 7.44 5.61 Li2CO3 Li2O 8.92 3.64 NaOH Na2O 1.99 1.55 SiO2 SiO2 22.15 22.35 Zr(OH)4.0.65H2O ZrO2 0.55 0.40 Na2SO4 Na2O 0.36 0.16 SO3 0.20 Bi2O3 Bi2O3 1.17 1.18 Cr2O3.1.5H2O Cr2O3 0.62 0.53 Ni(OH)2 NiO 0.50 0.41 PbO PbO 0.42 0.42 Fe(H2PO2)3 Fe2O3 1.25 0.40 P2O5 1.07 NaF Na2O 1.50 0.41 F 0.34 Na2CO3 Na2O 10.66 6.29 NaNO2 Na2O 0.35 0.16 NaNO3 Na2O 1.24 0.46 Na2C2O4 Na2O 0.13 0.06 CaSiO3 CaO 9.71 4.73 SiO2 5.07

Sum

141.366 100

Feed Compositions

FEED EXPANSION TEST PELLET PROFILE AREA AS A FUNCTION OF TEMPERATURE FOR 6 VARIATIONS OF THE HLW-A19 FEED (HARRIS ET AL., 2017)

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SLIDE 7

Ra Raw Material al Ox Oxide NG NG- Fe Fe2/100g wt wt%

Al(OH)3 Al2O3 8.61 5.63 H3BO3 B2O3 0.56 0.32 Na2B4O7.10H2O B2O3 37.16 13.57 Na2O 6.04 CaCO3 CaO 0.94 0.53 CeO2 CeO2 0.12 0.12 Cr2O3.1.5H2O Cr2O3 0.30 0.25 Fe Fe(OH)3 Fe Fe2O3 20. 20.54 54 15. 15.35 35 La(OH)3 La2O3 0.11 0.09 Li2CO3 Li2O 3.87 1.57 Mg(OH)2 MgO 0.24 0.17 MnO2 MnO2 3.98 3.98 NaOH Na2O 0.81 0.63 Na2CO3 Na2O 4.04 2.36 Ni(OH)2 NiO 0.59 0.48 FePO4.2H2O Fe2O3 1.71 0.88 P2O5 0.78 PbO PbO 0.63 0.63 Na2SiO3 Na2O 8.03 4.08 SiO2 3.95 Na2SO4 Na2O 0.39 0.17 SO3 0.22 SiO2 SiO2 37.33 37.33 SrCO3 SrO 0.28 0.20 ZnO ZnO 0.03 0.03 Zr(OH)4.0.654H2O ZrO2 1.57 1.13 NaNO2 Na2O 0.01 0.00 NaNO3 Na2O 0.45 0.16 H2C2O4.2H2O

  • 0.06
  • 132.36

100.64

In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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HLW-NG-Fe2 (Fe3+) HLW-NG-Fe2 (Fe2+) (Fe2+)

Ra Raw Material Ox Oxide NG NG- Fe Fe2/100g wt wt% Fe Fe(OH)3 Fe Fe2O3 20. 20.54 54 15. 15.35 35 Ra Raw Material Ox Oxide NG NG-Fe Fe2 (II)/100g wt wt% Fe FeC2O4.2 .2H2O Fe Fe2O3 34. 34.58 58 15. 15.35 35

7

Feed Compositions

  • Generic, simplified waste compositions
  • Specific waste streams with extreme levels
  • f waste oxides:

HLW-A19 HLW-NG-Fe2

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SLIDE 8

In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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Simplified HLW A-19 Composition

Oxide Raw Material mol% Target wt% XRF wt% Al2O3 Al(OH)3 16.73 25.13 29.16 B2O3 H3BO3 19.39 19.89 19.89 CaO CaCO3 6.63 5.48 3.20 Fe2O3 Fe2O3 3.47 8.16 10.04 Li2O Li2CO3 8.47 3.73 3.73 Na2O Na2CO3 10.42 9.52 7.26 SiO2 SiO2 31.73 28.09 26.71

HLW-A19 Simplified Stages of Melting Study

800oC 900oC 1000oC 1100oC 1150oC

99,65 99,7 99,75 99,8 99,85 99,9 99,95 100 100,05

1E-11 2E-11 3E-11 4E-11 5E-11 6E-11 7E-11 8E-11 150 300 450 600 750 900 1050

Mass/% Ion Current Temperature

OH H2O CO2 Mass/%

EVOLVED GAS ANALYSIS OF A-19 FEED BETWEEN 150℃ AND 1150℃(HARRIS ET AL., 2017) TG-MS OF SIMPLIFIED A-19 BATCH BETWEEN 150℃ AND 1150℃

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SLIDE 9

9 In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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800oC 900oC 1000oC 1100oC

HLW-A19 LSM Sample HLW-A19 Simplified Stages of Melting

2c 2cm

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SLIDE 10

10

CRYSTAL FRACTIONS IN HLW-A19 STAGES OF MELTING 100℃ TO 1200℃ (XU ET AL., 2016)

10 10

800oC 900oC 1000oC 1100oC 1150oC 1150oC + 1hr

Nepheline NaAl(SiO4) Magnetite Hematite Quartz In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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HLW-A19 LSM Sample HLW-A19 Simplified Phase Identification

800oC 900oC 1000oC 1100oC 1150oC 1150oC + 1 hour

Quartz Magnetite Hematite Nepheline

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SLIDE 11

In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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HLW-A19 LSM Sample EDX

Ba Backscattere d

Si Si Al Al Na Na

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SLIDE 12

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12

HLW-A19 LSM Sample EDX

Ba Backscattere d

Fe Fe Ni Ni Cr Cr

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SLIDE 13

In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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HLW-A19 Discussion

How well did the simplified stages of melting samples represent the cold cap sample?

  • Quartz dissolution
  • Iron phases
  • Gas-evolving reactions
  • Phases with other species, e.g. Ni, S, Cr
  • Evolution of nitrates and sulphates

Which reactions have been explored in both the simplified and complex feeds?

  • Evaporation of Water
  • Dehydration
  • Decarbonation and denitration
  • Low-viscosity melt forming
  • Formation of continuous glass forming melt
  • Primary foaming caused by mostly CO2 evolution
  • Primary foam collapse
  • Melt viscosity increases
  • Se

Secondary foaming

  • Dissolution of Quartz
  • Redox reactions and evolution of

f SO SO2

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HLW-NG-Fe2 Fast Dried Slurry Solids

NG-Fe2 Fe3+ NG-Fe2 Fe2+

In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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SLIDE 15

Stages of Melting Samples

NG-Fe2 Fe3+ NG-Fe2 Fe2+ 15 35 55 75 Intensity (a.u.) Angle (2θ) Fe3+1500 Fe2+ 1150 Fe3+ 1100 Fe2+ 1100 Fe3+ 1000 Fe2+ 1000 Fe3+ 900 Fe2+ 900 Fe3+ 800 Fe2+ 800

15

1mm 1mm

15 25 35 45 55 65 75 Intensity (a.u.) Angle (2θ) Fe3+1500 Fe2+ 1150

Quartz Unidentified Phase

In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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SLIDE 16

Feed Expansion Tests

  • 50
  • 45
  • 40
  • 35
  • 30
  • 25
  • 20
  • 15
  • 10
  • 5

Temperature Difference (μV)

9,43 4,73 1 2 3 4 5 6 7 8 9 10 50 150 250 350 450 550 650 750 850 950 1050 1150

Normalised Volume Temperature (oC)

NG-Fe2 Fe3+ NG-Fe2 Fe2+

Fe2+ Fe3+

16 In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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video video

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SLIDE 17

Laboratory Scale Melter

Feeding Glass Melting Quenching

200 400 600 800 1000 1200 00:00:00 00:10:00 00:20:00 00:30:00 00:40:00 00:50:00 01:00:00 01:10:00 01:20:00 01:30:00 01:40:00 01:50:00 02:00:00

Temperature (oC) Run Time

Plenum Glass Melt

1150oC

Feed slurry: NG-Fe2 Fe2+ (Iron Oxalate) Feed time: 40 mins Feed rate: 9rpm

17 In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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SLIDE 18
  • Using Ir

Iron Ox Oxalate (F (FeC2O4.2H2O) O) in place of Fe Fe(OH)3 as a raw material for the NG-Fe2 High Iron feed reduces the

  • verall amount of foaming.
  • Reduction of foaming may be due to the Fe redox state,

but may also be due to the hi highe her Ca Carbon co cont ntent nt– will be explored further by adding different amounts and sources

  • f

carbon as a reductant as well as Mössbauer spectroscopy on the samples.

  • Reduced Fe feed was su

success ssful in the Laboratory Scale Melter, and had reduced feed viscosity. Discussion: HLW-NG-Fe2

18 In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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Fe Feed Ra Raw Material Fe Fe Ox Oxidation State Fe Feed/100g wt wt% No Normal alised Vo

  • Vol. Increase

NG NG-Fe Fe2 (Fe Fe3+

3+)

Fe Fe(OH)3 3+ 3+ 20. 20.54 54 15. 15.35 35 9. 9.43 43 NG NG-Fe Fe2 (Fe Fe2+

2+)

Fe FeC2O4.2 .2H2O 2+ 2+ 34. 34.58 58 15. 15.35 35 4. 4.73 73

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SLIDE 19

Laboratory Scale Melter Sample

19

100oC 400oC 700oC 1000oC 1150oC

Plan:

  • SEM/EDX
  • Mossbauer Spectroscopy
  • Density/Porosity
  • X-ray Absorption Near Edge Structure

(XANES)

  • Thermogravimetric – Mass

Spectrometry

In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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SLIDE 20
  • 1. Explore effect of altering redox state of raw materials
  • n other feeds high in multivalent species e.g. HLW-E-

M09 (High-Cr)

  • 2. Spike simplified compositions with high amounts of

multivalent species (Ni, Mn, Cr, etc.) to understand redox effects on a more fundamental scale.

  • 3. Understand the effect of redox reactions on secondary

foaming and incorporate this into the wider models for heat transfer in the cold-cap Future Work

20 In Introduction Th Theory Exp Experimental Me Methods HL HLW-A1 A19 HL HLW-NG NG-Fe Fe2 Fu Future Wor

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21

Paul Bingham Anthony Bell Albert Kruger John Vienna John McCloy Kevin Fox Donna Post Gullien Richard Pokorný Ashutosh Goel David Peeler Derek Dixon Derek Cutforth Jamie George Pavel Hrma Seung Min Lee José Marcial

Th Thank k you for your atten ention, any y que questions ns?

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References

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  • 10. Hrma, P. R., & Pokorný, R. (2016). The Office of River Protection Cold Cap and Melt Dynamics Technology Development and Research Plan PNNL-25350. Richland,

WA.

  • 11. Hrma, P. R., Schweiger, M. J., Humrickhouse, C. J., Moody, J. A., Tate, R. M., Rainsdon, T. T., … Tincher, B. H. (2010). Effect of glass-batch makeup on the melting
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applicability for modeling the batch-to-glass conversion. Journal of the American Ceramic Society, 100(11), 5096–5106.

  • 14. Joseph, I., Bowan, B. W., Kruger, A. A., Gan, H., Kot, W. K., Matlack, K. S., & Pegg, I. L. (2010). High Aluminum HLW Glasses for Hanford’s WTP ORP-42448-FP. In

WM2010 Conference (pp. 1–13). Phoenix, Arizona.

  • 15. Lee, S., Hrma, P. R., Kloužek, J., Pokorný, R., Hujová, M., Dixon, D. R., … Kruger, A. A. (2017). Balance of oxygen throughout the conversion of a high-level waste

melter feed to glass. Ceramics International, 43(16), 13113–13118.

  • 16. Matlack, K. S., Gan, H., Chaudhuri, M., Kot, W. K., Pegg, I. L., Kruger, A. A., … Kot, W. K. (2012). Melter Throughput Enhancements for High-Iron HLW ORP-54002.

Washington, D. C.

  • 17. Matlack, Keith S, Viragh, C., Kot, W. K., Pegg, I. L., & Joseph, I. (2015). Effect of the Form of Iron on HLW Melt Rate VSL-15R3430-1. Washington, D. C.
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Glass Science2, 3, 59–68.

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